Secondary battery



(No Model.) A. V. MESEROLE.

- SECONDARY BATTERY. No. 359,877. Patented Mar. 22-, 1887.

Zjmvewhoz W W (M 3o current of nearly three volts elcctro-motive force, and maintaining its charge without ma- UNr r-En STATES 1 PATENT OFFICE.

ABRAHAM V. MESEROLE, OF NIHV YORK, Y., ASSIGNORTO .THE RIVER AND RAlL ELECTRIC LIGHT COMPANY, OF \VEST VIRGINIA.

SECONDARY BATTERY.

SPECIFICATION forming part of Letters Patent No. 359,877, dated March 22, 1857.

Application filed December 1, [8:36. Serial No. 220.398. (No model.)

. To all whom it may concern:

Be it knowuthat I, Animal-tn V. Mesnnouc, acitizen of the United States, residing at New .York, in the county and State of New York,

, have invented a new and useful Improvement in Secondary Batteries, which I desire to protect by Letters Patent of the United States,

I and of which the following is a specification, this application being designated by the letter terypossessing very remarkal 10 properties maybe constructed by immersing plates of zinc and lead in a cell containing a mercury solution, such as sulpnale of mercury, a zinc solution, such as sulphate of zinc, and tree sulphuric acid, the lead plate being preferably, but'not necessarily, amalgamated. If acne rent be passed through this cell from the lead (negative) to the zinc (positive) plate, a porous and highly absorptive layer of mercury and zinc will be formed on the positive plate, while at the same time the negativeplate is oxidized, the cell so prepared yielding in discharge a terial diminution for very considerable lengths of time. The action of this battery I conceive to be, in its principal outline, as follows:

During charge zinc and mercury are deposited on the positive plate, hydrogen at the same time being included in that deposit, and

peroxide of lead formed on the negative plate. If mercury is present on the negative plate, which is, as Ihave above stated, thought to be desirable, it will serve to replenish the solution, preventing the bath from being partially or wholly depleted of mercury, and promoting regular aetiom In discharge the occluded hy drogen, no'doubt, to some extent unites with the excess of oxygen on the negative plate, as

' in the Plant battery; but the current of discharge I believe to be principally due to the following moige complex reaction. 'The deposit of zinc and mercury breaks up and is redissolved,'th e zinc, by reason of its superior affinity, displacing the mercury in a part of the molecules of mercury sulphate. This displaced mercury in turn displaces hydrogen in the free sulphuric acid, which in turn draws oft the oxygen of the peroxidized negative plate. A part of the mercury set free is also, no doubt, thrown upon the negative plate in the form of anoxide. The electro-motive force of the cell should therefore be equal, speaking broadly, to that developed by the zinc replacing the mercury in the mercury sulphate supplemented by that developed by the liberated mercury in replacing hydrogen in the dilute sulphuric acid, and by the displaced' hydrogen in uniting with the oxygen of the peroxide.

The well-known Marie Davie primary battery has an electro-motive force of one and a halt volts developed by the displacement of.

is formed on the positive plate and of peroxide on the negative plate. The constancy of the secondary current depends upon the substantial character of these deposits, particularly that of the zinc-mercury sponge; .and the ow pacity of the battery to retain its charge, which it possesses in a very remarkable degree when properly formed, depends upon the presence of a considerable quantity of mercury on the positive plate. In this respect the'fanction of the mercury seems to be to prevent the free sulphuric acid of the bath from acting on the zinc of the positive plate.

In the ordinary zinc-lead accumulator the '1 free acid of the solution'coinbines with the zinc and large volumes of hydrogen aregiven off. This action takes place with the circuit open enclosed, and the deposit of zinc be ing thus rapidly redissolved, the cell soon becomes inactive. in my cell such action is prevented by the mercury present on the positive plate protecting the zinc from attack, except in discharge, and by the capacity oflhe zincmercury sponge to occlude hydrogen.

\Vhcn my cell isin perfect condition, noliydrogcn is given off either in charge or discharge, from which the in ferenee is clear that its liberation is prevented, or that it; is fixed oroccludcd in large quantities, or both in part, of which the last seems to he the most reason able hypothesis.

A further explanation of the remarkableelectro-motivo force of this battery maybe found in the superior capacity of the electrolytie zine-mercury sponge to occlude hydrogen and the peculiar qualities of the hydrogen so occluded, due to the conditions under which it'is taken up; and, again, the efficiency of the positive plate being for this reason ex- .ceptionally great, it; is probable that superior efficiency is induced thereby in the nc ative plate, causing an exceptionally favorableoxidation of the latter plate. I am inclined to believe that in the process ofcharging, oxygen I in the form of ozone is taken up on the negative plate, and that the clectro-motive force exhibited may be iu part due to this fact.

ll'aving thus given a general view of my improved battery in what 1 now believe to be its best form, and having indicated in general my theory of its action, I shall now advert to certain subsidiary peculiarities of its action, and suggest certain modifications which may enable the gist of my invent ion to be seen in a. clearer light.

As to the metal used for the. negative plate, it is only requisite that it becapable of taking up oxygen to excess. lly reason of cheapncss and its other suitable qualities 1 have found lead to be the most available material; but it is evident that. any conducting metal capable of taking up-and givingoff oxygen readily would be in this battery the equivalentoflead.

As abovesuggcsted, the function of the positive plate, whcrczinc is used in the solution,

is only to furnish a conducting support for' the zinc-mercury deposit. Any metal, therefore, capable of performing this function would be an equivalent of the zinc plate in my cell. 1 have lound that in use a pos tiie plate made up of thin exterior sheets of zinc baeltcd or tilled with lead is the most satistactory.

As 1 have indicated above, an important part is played in my battery by the spongy porous zinc-mercury deposit; and while 1 tie sire to claim and protect herein the described process of producing that deposit, 1 wish it understood that I also claim its use in an accnmulatinn-battery however it may be ob taincd; and, also, 1 claim the described process independently of the particular form or ehcmi-' cal composition of the resulting batteryplate. This deposit is altogether different in character from anamalgamated zinc-plate. The latter has a smooth and polished surface not 'elect-romotive force exhibited.

at all adapted to the occlusion of hydrogen, while the electrolytically-formed surface described is more or less rough, crystalline, and spongy in appearance. There are doubtless a considerable variety of ways iuwhich it may be obtained besides that which has been herein described. Thus sulphides or oxides of mcrcury and zinc, with or without the addition of finely-divided pure metal, might be pressed into proper form or applied to a proper supporting, and conducting structure and reduced to the condition of spongy metal by electrolytic action in a suitable bath, the current in such case being aided by local chemical action. I have, in fact, found by experiment that this is a fairly effective way to form the battery, though inferior to that first described; and I sometimes also apply mercury and-lead oxides or sulphides to the negative plate, which will more readily attain high oxidation than pure nu-tal. So, too, it would perhaps be practicable to make a mechanical mixture of .zinc. and mercury for thepositive plates,

grinding up these metals, mixing them in suitable proportions, and pressing them into proper shape, and forming them tip electrolyticallyiu the manner suggested for the treatment; of sulphides aml oxides. So, too, the materials may be placed in porous cups or saucers, the deposit being in this case'formed on the top surface of tho'liquid.

l have selected zinc as a constituent element of my battery for the reason that it gives a highly electropositive action, and also because the zine-mercury combination is passive in the solution when no current is flowing; but any posing;- the electrolyte.

i believe thatin actual use sulphides and .Sulphates of '/.ine, mercury,and lead are formed on-the two batteryplates, as well as the various oxides of those metals, and it is p'robablcthat; their presence has an ell'ect relative to thehigli I wish it understood, therefore, that I regard the metalsin these forms as equivalents in my battery ofpure spongy metal'.

While, as above stated, any material may be used for the positive plate which will act as a conducting support for the mercury-zine deposit, still l believe a zinc plate to be preferable, for the reason that a deposit of zine is more readily made upon a zinc plate than upon a plate of any other material, and enters into closer. and more compact union with the plate than it would were the plate of other material. For thisreason, asstatedflconsider a thin plate of zinc furnished with the requisite strength by backing of lead or other conducting material to be the best form of plate.

With regard to the action of my battery, I should further say that I believe the mercury upon the negative plate to have'a valuein the battery as an active material, especially when electrolytically deposited, as in my cell, and, further, that its presence on that plate facilitates oxidation and deoxidation of the other active materials of that plate, adding in this way to the electro-motive force of the cell; and, further, that there are -probably reactions among the various salts and basic compounds of mercury which are formed in the cell, and between these salts and bases and the other materials contained in the cell, which are too obscure to be followed theoretically. I therefore do not rest my application upon the explanation advanced, although it is the best which I am now able to offer, and I believe it to correspond with the facts. I proceed upon the supposition that my patent will be construed to cover the battery I have invented, whether or not the theory of its action advanced proves to be, in whole or in part, accurate.

In the drawing annexed my invention is conventionally illustrated, A being the cell, B andO the positive and negative pole-pieces, respectively, and D a thin zinc plate forming a part of the positive plate.

In my use of the term single fluid as applied to secondary batteries in this application for patent I intend to distinguish between a battery of the sort shown herein and a battery having multiple electrolytic fluids, in which latter class I place all batteries in which the two electrodes are immersed respectively in solutions differing from each other in chemical composition and chemical equivalency, and in which the separation of these solutions from each other is maintained bya porous partition or the like. 'I intend to include all other seeondarybatteries under the term single fluid secondary batteries.

I reserve the right to file another application for Letters Patent for, and do not hereby dedicate to the public, the following subject-matter: first, in a secondary battery, an electrolytically-deposited activelayer of mercury and zinc; second, a secondary battery in which all the active material on one of the pole-pieces is an electrolytical formation of mercury and zinc; and third, the herein-described process of forming electrodes by the electrolytic treatment of sulphides or oxides of zinc and mercury.

By the word plates in this applicationI mean to include all forms of electrodes or polepieces.

Having thus described my invention, what I claim, and desire to protect by Letters Pat: ent, is-

1. The improvement in preparing secondary batteries which consists in forming up the positive and negative pole'pieces or plates by immersing them in a single-fluid bath of mercury and zinc solutions and passing an electrical current through them and the liquid.

2. Theimprovementinpreparingsecondary batteries which consists in forming up zinc and lead plates, therefor by immersing such plates in a single-fluid bath containing a solution of mercury and passing an electrical current through them and the bath.

3. Theimprovementinpreparingsecondary batteries which consists in immersing the platesin a single-fluid bath containing mercury and zinc in solution, together with a free acid, and forming up the same for use by passing an electrical current through the plates and the bath.

4. A secondary battery in which both plates are immersed inan electrolyte which contains sulphate of mercury and the positive plate or pole-piece is composed wholly or in part of zinc.

5. A secondary battery in which both plates are immersed in an electrolyte composed of a solution of mercury mixed with a solution of zinc, with or without free acid.

6. A secondary battery in which both plates are immersed in an electrolyte composed of sulphate of mercury and sulphate of zinc,with or without free sulphuric acid. I

7. In a secondary battery, a positive polepiece made up of a thin zinc plate backed by a supporting-plate of lead or other conducting material.

8. A single-fluid secondary battery in which the electrolyte contains a substantial working quantity of mercury in solution and the positive plate is formed in Whole or in part of zinc, substantially as set forth.

9. A secondary battery having asingle electrolytic fluid in which the active material of the positive element consists of an electrolytically-formed layer of zinc and mercury, substantially as set forth.

10. A single fluid secondary battery in which the active material of the positive plate is electrolytically-combined zinc and mercury and the active material of the negative plate is oxidized lead, substantially as set forth.

11. A single fluid secondary battery in which the active material of the positive plate consists of zinc and mercury electrolytically combined and the active material of the negative plate consists of lead and mercury, .substantially as set forth.

12. A single fluid secondary battery in which the active material of the positive plate is mercury electrolytically combined with zinc and the electrolyte whereof contains mercury in solution, substantially as set forth.

13. A single fluid secondary battery in which the active material of the positive plate consists of mercury electrolytically combined with zinc and the electrolytic fluid whereof contains mercury and zinc in solution, sub- I stantially asset forth.

14. A single-fluid secondary battery in which the active material of the positive plate consists of mercury electrolytically combined with zinc, the active material of the negative plate is lead and the electrolyte whereof contains mercury in solution, substantially as set forth.

15. A single-fluid secondary battery wherein the active material of the positive plate 

